Anthraquinone compounds



Patented Jan. 18, 1949 UNITED STATES PATENT OFFICE ANTHRAQUIN ON E COMPOUNDS Harry W. Coover, Joseph B. Dickey, and Edmund B. Towne, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application June 1, 1945, Serial No. 597,162

This invention relates to anthraquinone compounds useful for the coloration of textile materials containing cellulose carboxylic ester rayon, and to a process for the preparation of such dyes.

The anthraquinone compound having the formula:

O TGIF-CH has long been known. This compound, however, is of little value as a dye for textile materials containing cellulose carboxylic ester rayon, because it colors such textile materials very poorly from an aqueous suspension of the compound. Similarly, the anthraquinone compounds having the following general formula:

ester rayon textile material because they color r such textile materials poorly from their aqueous suspensions. Further, the dyeings obtained, in general, are not as light fast as those obtained using 1-methyl-amino-4-phenylamino anthraquinone.

Another known anthraquinone compound, 1- amino-4 -p- (hydroxyphenyl) -amino anthraquinone having the formula:

11 is of little value for coloring cellulose oarboXylic ester rayon textile materials because it colors such materials poorly from an aqueous suspension of the compounds.

2 Claims. (01. 260-380) The known compound, 1,4-di(p-tolyl)amino anthraquinone, having the formula:

possesses so little affinity for celulo'se carboxylic ester rayon textile materials that it is unquestionably not a dye for such materials.

Still another known c mpound having the formula:

H a) I]-I--CHA dyes cellulose carboxylic ester textile materials fairly well, but the dyed textile materials leave much to be desired with respect to resistance to gas-fading and fastness to light. The dyeings obtained with this dye compound are about half as fast to light and about half as resistant to gasfading as are the dyeings obtained with our new dye compounds.

Other anthraquinone compounds having the following general formula:

H O i l Y1 wherein Y and Y1 each represents methyl, ethyl, propyl, butyl, s-hydroxyethyl, p-hydroxypropyl or flJ-dihydroxypropyl, for example, color cellulose acetate very readily but again the dyed materials leave much to'be desired with respect to resistance to gas-fading and fastness to light. The dyeings obtained with our new title omp unds on cellulose carboxylic ester rayon textile materials are approximately 200-300% faster to light and approximately better with respect to gas-fading than the dyeings obtained on these materials with the dye compounds just mentioned.

The anthraquinone compounds, which we believe are new compounds, having the following wherein Z represents an alkyl group such as methyl, ethyl, propyl or butyl', an alkoxyalkyl group such as e-methoxyethyl or c-ethoxy-ethyl or a hydroxyalkyl group such as i3-hydroxyethyl, 18-hydroxy-propyl, y-hydroxypropyl or pJ-dihy- .droxypropyl possess some afhnity for cellulose carboxylic esterrayontextile materials. The greenish-blue dyeings obtained with these compounds possess good resistance to gas-fading as well as good fastness to light. Their affinity for cellulose carboxylic textile materials, however, is a not nearly as good as that of the new anthraquinone compounds of our invention.

We have now found new, anthraquinone compounds which not only dye cellulose carboXylic ester rayon textile materials readily to full shades, but the dyed textiles aremuch more re si'stant to gas-fading than are textiles colored with the aforesaid prior compounds, and are also as light-fast, or faster, than'are the textiles dyed with the aforesaid prior compounds. Our new anthraquinone compounds color cellulose carboxylic ester rayon textile materials greenishblue shades which are of considerable industrial value. They are of particular value for the 40 coloration of cellulose acetate rayon textile materials. It is, accordingly, an object of our invention to provide new anthraquinone dye compounds and to provide a process for preparing such dye compounds Other objects will become apparent hereinafter.

Ournew anthraquinone compounds can be represented by the following general formula:

wherein n represents a whole positive integer of from 1 to 2, D represents an ethylene group, a

trimethylene group or a propylene group, Q

represents a phenylenegroup (e. g. o-phenylene and p-phenylene groups) which may carry substituents, such as halogen, an acetamino group, a methyl group, a hydroxyl group, an alkoxy group,-a trifluoromethyl group, et .c., R represents la memberselected from'the'group' consisting of anthraquinone compound of the following general formula:

(d N -lh halogen wherein R1 represents a low carbon allzyl group, a low carbon alkoxyalkyl group or a low carbon hydroxyalkyl group with an amino compound of the following general formula:

wherein n represents a whole positive integer of from 1 to 2, Q represents a phenylene group which may carry substituents such as halogen, an acetamino group, a methyl group, a hydroxyl group, an alkoxy group, a trifluoromethyl group. etc., D represents an ethylene group, a trimethylene group or a propylene group and R represents a member selected from the group consisting of hydrogen and an alkyl group containing from '1 to 2 carbon atoms.

The condensation reaction just mentioned is advantageously carried out in the presence of the ammonium salt of a low carbon aliphatic fatty acid. The use of ammonium acetate is preferred. Ammonium acetate or its aqueous solutions can be used as such, but we havefound a stock solution of acetic acid, water and ammonia, the ammonia and acetic acid being present in equal molecular proportions, to be a most convenient form in which to apply the ammonium acetate. The ammonium salts of other low carbon. aliphaticfatty acids may be similarly conveniently employed,

e. g,,a stock solution of propionic acid, water and ammonia, the ammonia and propionic acid'being present in equal molecular proportions, can be used. The function, for example, of ammonium acetate is not known to us but we have found its presence definitely beneficial. The term ammonium salt of a low carbon aliphatic fatty acid as used herein and in the claims refers not only to the salts but also to solutions containing both a low carbon aliphatic acid and ammonia.

Similarly, the condensation reaction is advantageously carried out in the presence of a copper catalyst. Cupric acetate and cupric sulfate have been found to aid in the reaction. Of these the use of cupric acetate is preferred.

Our new anthraquinone compounds can also be prepared by reacting the leuco derivatives of the anthraquinone compounds of the following general formula:

;pound of the formula:

wherein n, D, Q and B. have the meaning assigned dium or diluent which is inert with respect to the condensation. Alcohols, especially alcohols of the formula: CnH2n+10'H wherein n represents a positive integer of from 2. to 5 are advantageously employed as the diluent. Tetrahydro- :furfuryl alcohol or pyridine can be employed as the diluent. Heat accelerates the condensation.

Following the condensation, the lance compound is oxidized in any of the known manners of oxidizing leuco compounds, e. g, by passing air through the reaction medium or preferably by means of an oxidizing agent, such assodium perborate.

The following examples illustrate our new anthraquinone compounds and the manner of ob taining the same.

3 grams of 1-methylaminol-bromoanthraquinone, grains of p{fi- [,B-({3-hydroxyethoxy) -ethoxyl-ethoxy}-aniline, 0.1 gram of cupric acetate and cc. of astock solution containing cc. of glacial acetic acid, 400 cc. of water and cc. of 28% aqueous ammonia were placed together in a suitable reaction vessel. The reaction mixture was slowly heated to boiling with vigorous stirring and boiling and vigorous stirring were maintained until no further color change took place. When cool the reaction mixture was filtered and the dye of the above for mula was obtained as an insoluble product. It was washed with cold dilute 23% hydrochloric acid. Upon crystallization from butanol the dye melted at C. t colors cellulose acetate greenish-blue shades from its aqueous suspensions.

In a similar manner, l-methyla1nino--lo- {,B-[flJfi-hydroxyethoxy) ethoxylethoxy}- anilino anthraquinone, l-methylamino 4 {p- [a ([i-hydroxyethoxy) ethoxy] anilino} anthra quinone, l-methylainino 4-{ o-chloro-p-lp mhydroxyethoxy) ethoxy] aniline} anthraquinone, 1 methylamino-4-{p-[v poxy) propoxy] anilino} anthraquinone, 1

- (y-hydroxypro- 6 methylamino 4-{p- 9- (p-hydroxypropoxy) -propoxy] -anilino} -anthraquinone, 1 methylamino- 4 {p acetamino o [,6 (B hydroxyethoxy)- ethoxy] anilino} anthraquinone, 1 methyl- 5 amino-l-{p-[fl-(fl-ethoxyethoxy)-ethoxy] anilino}-anthraquinone and 1 methylamino--{p- [fl (c methoXy-ethoxy) -ethoxyl-anilino}-anthraquinone can be prepared. Emample 2.--1-ethylamino-4- p {c- [18- 3 hy- 10 drowyethoxy)-ethowl-etho.ry} anz'lz'no -anthraqumone H 1 r-o2m 9 grams of 1-ethylamino-4-bromoanthraquinone, 30 grams of p-{fi-[.B-(c-hydroxyethoxy)- ethoxy]-ethoxy}-aniline, 0.3 gram of cupric acetate and 60 cc. of a stock solution containing loo cc. of glacial acetic acid, 400 ccoof water and 1.10 cc. of 28% aqueous ammonia are placed together in a suitable reaction vessel and the reaction mixture is slowly heated to boiling with vigorous stirring and boiling and vigorous stirring are maintained until no further color change takes place. When cool the reaction mixture is filtered to obtain the dye of the above formula as an insoluble product. The dye is washed with cold dilute 2-3% hydrochloric acid and then with water. It colors cellulose acetate greenish-blue shades.

In a similar manner l-ethylamino-4- o-hydroxy p -{B- [54,8 hydroxyethoxy) ethoxylethoxy}-anilino -anthraquinone, l-ethylamino- 4 {o-methyl-p- [,6- (p-hydroxyethoxy)-ethoxyl pylamino-4.-bromoanthraquinone and l-n-butylamino-4-bromoanthraquinone for the l-methybalninoi-bromoanthraquinone of Example 1, l p-methoxyethylamino-4- p-{p- [p 8 hydroxy ethoxy) -ethoxyl-ethoxy} anilino u anthraqulnone, l-isopropylaminolp- {c- [B- (p-hydroxyethoxy) -ethoxyl-ethoxy} anilino anthraquinone, l-fm dihydroxypropylainino i p-{/3[fi (,c-hydroxyethoxy)-ethbxylethoxy} anilino anthraquinone and 1-n-butylamino-4- p-{/3-[p (B-hydroxyethoxy) -ethoxyl ethoxy} anilino anthraquinone, respectively, can be prepared.

7 8 Example 3.-1-B-methoxyethylamino-4- p-{5- droxyethoxy)-ethoxy]-anilino anthraquinone, lic-(p-hydromyethomy) ethoryl-ethory}-anil-fi-hydroxyethylamino 4- p-{[3-[p-( 6-hylino -anthraquinone droxyethoxy) -ethoxyl ethoxy} anilino anl I g-O-o-onrcrn-o-om-cm-om-cm-on 12 grams of leuco quinizarin and 200 cc. of butanol thraquinone, l-B-hydroxyethylaminol-{p- [fi-(B- are put in a suitable reaction vessel and heated 15 hydroxyethoxy) ethoXyl-anilino}- anthraquitogether to refluxing conditions with vigorous none, l-n-propylamino-lp-{{3-[B-(p-hydroxystirring. 7.5 grams of B-methoxyethylamine in ethoxy)-ethoxy]-ethoxy}-anilino anthraqui- 50 cc. of butanol are then added dropwise over none, l-isopropylaminop-{B-[B-(fi-hya period of 1 hour, following which 6 grams of droxyethoxy)-ethoxy1-ethoxy} ani1ino anboric acid are added. Then 12 grams of p-{B- [B- thraquinone, l-[3,y-dihydroxypropylamino-4- p- (Zfl-hydroxyethoxy) -ethoxyl -ethoxy}-aniline in {5- cfi-hydroxyethoxy) -ethoxy] -ethoxy}- ani- 50 cc. of butanol are added to the reaction mixture lino -anthraquinone, l-Ay-dihydroxypropylaand the refluxing is continued, with stirring, for mino-4- p-{fi-[p-(,c-ethoxyethoxy) ethoxylabout 10 hours. The resulting leuco dye comethoxy} anilino anthraquinone, 1 findihypound is oxidized by adding an aqueous solution droxypropylaminc-4 -{o-[c-(,e-hydroxyethoxy).- of sodium perborate to the hot reaction mixture. ethoxy] anilino} anthraquinone, 1 fin dihy- After cooling the reaction mixture is poured into droxypropylaminolE p-{y- [v-(y-hydroxyprowater to precipate the dye which is recovered by poxy) -propoxyl propoxy}-anilino -anthraquifiltration, washed with water and dried. If desired none, 1-n-butylaminolp-{fi-lfi-(B-hydroxythe dye may be purified by one or more crystalliethoxy) ethoxyl-ethoxy}-anilino anthraquizations from a solvent, especially where a dye none and l-n-butylaminol-{p-[p-(p-hydroxycompound of high purity is desired. Where more ethoxy) -ethoxyl-anilino}-anthraquinone can be than one crystallization is used the second crysprepared.

tallization, can, of course, be effected from a dif- Likewise in accordance with our invention 1- ferent solvent than that used in the first crysmethylamino--{o-methoxy p-[B-(fi-hydroxytallization. Upon purification by recrystallizaethoxy) ethoxy] anilino} anthraquinone, 1- tion from butanol the dye compound melts at ethylamino-e-{p-hydroxy-o [Ii-(fi-hydroxyethl27-130 C. It colors cellulose acetate greenishoXy] aniline} anthraquinone, 1 ethylblue shades. amino--{p-[p-(fi-hydroxypropoxy) propoxyl- Boric acid can be omitted from the condensaanilino}-anthraquinone, l-b-hydroxyethylamition reaction of Example 3 with little change in n0-4-{p-[B-(B-methoxyethoxy)-ethoxyl anithe results obtained. lino}-anthraquinone, l-p-hydroxyethylaminol-B-methoxyethylaminolp-{fl-[ 8 (p hylotrifluoromethyl-p {fi-[B-(B-hydroxyethdroxyethoxy) -ethoxyl ethoxy} anilino anoxy) -ethoxy] -ethoxy}-anilino -anthraquinone,

thraquinone can also be prepared in accordance 1-fi-hydroxyethylamino-4 p {[3 [c (ii hywith the method described in Example 1 or 2 by droxypropoxy) propoxyl propoxy} anilino condensing 1 fi-methoxyethylamino-4-bromoanthraquinone, 1-isopropylamino-4-{p-[fl-(p-hyanthraquinone with p-{p-lfi-(c-hydroxyethdroxyethoxy)-ethoxyl-anilino}- anthraquinone, oxy) -ethoxy] -ethoXy}-aniline. 1 -isopropylamino-4 {0- lp-(p-hydroxyethoxw- 0 ethoXy] aniline} anthraquinone, 1 isopropylamino-4 {p- -(v-hydroxypropoxy) -pr0poxyl anilino}-anthraquinone and l-n-propylamino-4- {p-[p-(fi-ethoxyethoxy) -ethoxyl anilino} an- 13.35 grams of 1-ethylamino-4-hydroxyanthraquinone can be prepared.

thraquinone, 30 grams of p-{fi-[p-(B-hydroxy- 5 l-(alkyl, alkoxyalkyl, hydroxyalkyl) amino-4- ethoxy) ethoxyl -ethoxy}-aniline and 6 grams of halogen anthraquinone compounds can be preboric acid are refluxed together in pyridine until pared by halogenating a l-(alkyl, alkoxyalkyl, no u th r color change takes place, a ly hydroxyalkyl) amino anthraquinone. These lat- 15-20 hours. Upon cooling the reaction mixture ter anthraquinone compounds can be prepared,

is filtered to obtain the dye as an insoluble prodfor example, by reacting l-chloroanthraquinone 5 Example 4.1-ethyZamino-4 p-{B-[B ([3 hydroxyethoxy) -etho:cyl-ethoacy}- anilin0 cmthraquinone uct. The dye is washed with an aqueous 2% ina diluent medium inert under the reaction conhydrochloric acid solution to remove unreacted ditions employed with an alkylamine, alkoxyp-{c-[ s-(e-hydroxyethoxy) ethoxyl ethoxy}- alkylamine or a hydroxyalkylamine in the presaniline, washed free of acid with water and then ence of cupric acetate. The manner of preparawashed with dilute aqueous sodium hydroxide tion of these l-(alkyl, alkoxyalkyl, hydroxyalkyl) to remove any unreacted l-ethylaminoi-hyamino anthraquinone compounds will be appardroxyanthraquinone. The dye is then washed ent from the following.

with water to remove any sodium hydroxide present. It colors cellulose acetate greenish-blue Preparation of 1'memylammoanmmqumone shades. 122 grams of l-chloroanthraquinone, 500

Similarly following either the procedures of grams of pyridine, 148 grams of a 25% solution Examples 1 and 2 or of Examples 3 and 4, l-pof methylamine in water and 1 gram of cupric methoxyethylaminol-p-lfi (B-ethoxyethoxy)- acetate are heated together in a shaking autoethoxyl-anilino anthraqulnone (M. P. -112 clave'at C. for six hours. The autoclave is C.), l-B- methoxyethylamino 4-0 [,B-(B-hy- 76 then cooled to room temperature and its contents poured into two liters of water. The reaction mixture is filtered, washed with water and dried. l-methylaininoanthraquinone melting at 167 is obtained with a yield of about 95 Similarly, the following have been prepared:

a m i n o anthraqulnone anthraquinone (M. P.

l-ethylamino anthraqulnone (M. P. l23-l24 C.) a

The manner of preparation of the l-(alkyl, alkoxyalkyl, hydroxyalkyl) amino-e-halogen anthraquincne compounds, is illustrated hereinafter. i

Preparation of 1-methylamino-4-bromoanthraquinone 47.4, grams of l-methylarnino anthraquinone are dissolved in 500 cc. of pyridine and theresulting reaction mixture is heated on a water bath to 60 C. with stirring. At this temperature there is added to the reaction mixture, which is contained in a suitable reaction flask, 33.2 grams excess) of bromine over a period of 1 /2 hours. The reaction mixture is then slowly heated to 90-95 C. and kept there for two hours, filtered hot and allowed to cool overnight. Stirring is maintain-ed throughout the period of heating. The cooled reaction mixture is filtered to recover the lonethylamino-d-bromoanthraquinone which is washed with 100 cc. of pyridine and dried. The product obtained melts at 193-195 C Similarly, c hydroxyethylamino-4-bromoanthraquinone (ll/l. P. 170 (3.), l-BJ-di-hydroXypropylamino-4-bromoanthraquin-one (M. P. 145 C), l-,8-methoxyethylamino-l-bromoanthraquinone (M. P. 152 0.), and l-isopropylamino-lbromoanthraquinone (M. P. 222 C.) have been prepared.

The aniline derivatives of the following formula:

wherein n represents apositive integer of from 1 to 2, Q represents a phenylene group, D represents an ethylene group, a trimethylene group or a propylene group and R represents a hydrogen atom or an alkyl group of from 1 to 2 carbon atoms can be prepared by condensing a chloronitrobenzene derivative of the following formula:

wherein Q represents a phenylene group which may carry substituents such as halogen, an acetamino group, a methyl group, a hydroxyl group, an allioxy group, atrifiuorom-ethyl group, etc., with a sodium alcoholate of the following formula:

wherein D represents an ethylene group, a trimethylene group or a propylene group, n represents a positive integer of from 1 to 2, and R represents hydrogen or an alkyl group containing from 1 to 2 carbon atoms, and then reducing the resulting nitro compound with hydrogen, in the presence of a nickel catalyst, especially of the with trimethylene chlorohydrin. ,30

the alcoholsof the formula:

H-OD-(O-D) n-O-R wherein D represents an ethylene group, a trimethylene group or a propylene group, n represents a positive integer of from 1 to 2, and R represents hydrogen or an alkyl group of from 1 to 2 carbon atoms. Many of these alcohols are very well known substances and readily available on the market, e. g. diethylene glycol and triethylene glycol and the monomethyl and monoethyl ethers of these glycols. Dipropylene glycol is also available on the market. Tripropylene glycol can be prepared by reacting 10 moles of dipropylene glycol with one mole of sodium and condensing the resulting mixture with one mole of propylene; chlorohydrin (CHsCHOl-ICHzCl) Dit1-in1etl1ylene glycol can bet-prepared by reacting 10 moles of trimethylene glycol with one mole of sodium and condensing the resulting mixture Tri-trimethylene glycol can be prepared by reacting 10 moles of di-trimethylene glycol with one mole of sodium and condensing the resulting mixture with one mole of trimethylene chlorohydrin. The monomethyl and monoethyl others of diand tri-propylene glycol and of di-trimethylene glycol and tri-triinethylene glycol can be prepared by reacting 5 to 10 moles of the glycol with sodium and condensing the resulting mixture with methyl iodide or ethyl iodide.

The anthraquinone dyes of our invention are especially useful for the coloration of organic derivatives of cellulose which include the hydrolyzed, as well as the unhydrolyzed, cellulose carboxylic esters, such as cellulose acetate, cellulose propionate and cellulose butyrate, and the hydrolyzed, as well as the unhydrolyzed, mixed carboxylic esters of cellulose, such as cellulose acetate-propionate and cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellu lose, ethyl cellulose and benzyl cellulose. Our new dyes are also useful for the coloration of cellulose ester and cellulose ether lacquers, as well as lacquers made from polyvinyl compounds. Our new dyes can be used to color nylons and textiles prepared therefrom.

The anthraquinone dyes of our invention can be applied to the coloration of fabrics made of or containing organic derivatives of cellulose,

such as cellulose acetate rayon, by the known dyeing or printing methods. In accordance with the known dispersion method ofdyeing, the anthraquinone dyes are first ground to a fine powder, intimately mixed with a suitable dispersing or solubilizlng agent, following which the resulting mixture is added to water or a dilute solution of soap in water to form an aqueous dye bath. The textile materials are then immersed in such a dye bath in accordance with known procedures. Suitable dispersing or solubilizing agents include soap, sulforicinoleic acid, the alkali metal salts of sulforicinoleic acid, sulfonated oleic, stearic or palmitic acid or salts thereof, such as the sodium or ammoniumsalts.

In accordance with the recommendations of Chemical Abstracts, the term propylene is in- 12 tended. to mean the 'group having the following 2. The anthraquinone dye compound having formula: the formula:

-CHa-OH- H 'N-CH: Ha I and the term trimethylene is intended to'mean the group having the following formula: &

-CHzCH2-CH2- v l i We claim: IfiI-O-O-OHaCHz-O-CHgCHg-O-GHs 1. The anthraquinone dye compounds having HARRY W COOVER the general formula: 2 JOSEPH DICKEY 5 EDMUND B. TOWN'E.

o N-om 1 g I 1 REFERENCES CITED The following references are of record in the file of this patent: UNITED STATES PATENTS A gC O-CHzCHa(OCH:CH2)u-O-R Number Name Date 2,210,517 Wilder Aug. 6, 1940 2,242,760 Schoeller May 20, 1941 wherein n represents a whole positive integer 2,326,047 McNally 'et a1 Aug. 3, 1943 of from 1 to 2 and R represents an alkyl hydro- 2,338,908 Dickey et a1 Jan. 11, 1944 carbon group containing from 1 to 2 carbon 2,353,108 Wuertz et a1 July 4, 1944 atoms. 2,357,176 Dickey Aug. 29, 1944 

